Qiao Junyi, Zhang Borong, Yu Xueyue, Zou Xiaoqin, Liu Xinyao, Zhang Lirong, Liu Yunling
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, P. R. China.
Key Laboratory of Polyoxometalate Science of Ministry of Education, Northeast Normal University, Changchun 130024, P. R. China.
Inorg Chem. 2022 Feb 28;61(8):3708-3715. doi: 10.1021/acs.inorgchem.1c03924. Epub 2022 Feb 15.
Here, a Y(III)-based metal-organic framework, {[Y(μ-O)(μ-OH)(HO)(BTCTBA)]·2[(CH)NH]·5DMF·CHCl·4HO}, has been successfully synthesized under solvothermal conditions. was constructed with amide-functionalized tricarboxylate ligands and Y(III)-based infinite chains, where the Y repeating units are arranged in a order. The overall framework could be viewed as a novel (3,5)-connected net with two types of channels along the [100] and [010] directions. possesses a large BET surface area (1553 m g), a permanent pore volume (0.67 cm g), and outstanding thermal and chemical stability, which give potential for the purification of natural gas, especially the equimolar separation of CH/CH with a high selectivity of 176. In addition, benefiting from the amide functional groups as Brønsted basic sites and the exposure of open metal sites as Lewis acid sites after activation, can serve as a high-efficiency heterogeneous catalyst for Knoevenagel condensation by the reactions of malononitrile with benzaldehyde (yield of 98%, turnover number of 392, and turnover frequency of 3.27 min) and diverse aldehyde compounds. A rational mechanism was put forward that the Knoevenagel condensation was catalyzed by the synergistic effect of the Lewis acid sites and Brønsted basic sites, engendering the polarization of the carbonyl groups and the deprotonation of the methylene groups for nucleophilic attack.
在此,一种基于Y(III)的金属有机框架{[Y(μ-O)(μ-OH)(HO)(BTCTBA)]·2[(CH)NH]·5DMF·CHCl·4HO}已在溶剂热条件下成功合成。它由酰胺功能化的三羧酸配体和基于Y(III)的无限链构建而成,其中Y重复单元按一定顺序排列。整体框架可视为一种新型的(3,5)连接网络,沿[100]和[010]方向有两种类型的通道。它具有较大的BET表面积(1553 m g)、永久孔体积(0.67 cm g)以及出色的热稳定性和化学稳定性,这使其具有用于净化天然气的潜力,特别是对CH/CH的等摩尔分离,选择性高达176。此外,得益于酰胺官能团作为布朗斯台德碱位点以及活化后开放金属位点作为路易斯酸位点的暴露,它可作为一种高效的多相催化剂用于丙二腈与苯甲醛的反应(产率98%,周转数392,周转频率3.27 min)以及多种醛类化合物的Knoevenagel缩合反应。提出了一种合理的机制,即Knoevenagel缩合反应是由路易斯酸位点和布朗斯台德碱位点的协同作用催化的,导致羰基极化以及亚甲基去质子化以进行亲核攻击。